全文获取类型
收费全文 | 3287篇 |
免费 | 32篇 |
国内免费 | 82篇 |
专业分类
化学 | 155篇 |
晶体学 | 1篇 |
力学 | 88篇 |
综合类 | 28篇 |
数学 | 2869篇 |
物理学 | 260篇 |
出版年
2024年 | 3篇 |
2023年 | 10篇 |
2022年 | 26篇 |
2021年 | 17篇 |
2020年 | 41篇 |
2019年 | 27篇 |
2018年 | 21篇 |
2017年 | 40篇 |
2016年 | 52篇 |
2015年 | 59篇 |
2014年 | 130篇 |
2013年 | 327篇 |
2012年 | 159篇 |
2011年 | 213篇 |
2010年 | 141篇 |
2009年 | 248篇 |
2008年 | 186篇 |
2007年 | 230篇 |
2006年 | 188篇 |
2005年 | 128篇 |
2004年 | 109篇 |
2003年 | 92篇 |
2002年 | 101篇 |
2001年 | 125篇 |
2000年 | 88篇 |
1999年 | 75篇 |
1998年 | 72篇 |
1997年 | 58篇 |
1996年 | 61篇 |
1995年 | 40篇 |
1994年 | 17篇 |
1993年 | 17篇 |
1992年 | 15篇 |
1991年 | 12篇 |
1990年 | 9篇 |
1989年 | 13篇 |
1988年 | 10篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 50篇 |
1984年 | 48篇 |
1983年 | 19篇 |
1982年 | 38篇 |
1981年 | 33篇 |
1980年 | 25篇 |
1979年 | 15篇 |
1978年 | 4篇 |
排序方式: 共有3401条查询结果,搜索用时 534 毫秒
61.
3,3′:4′,3″-Ter-1,2,5-thiadiazole, an useful oligoheterocyclic compound, has been accomplished in seven steps from 1-(5-methyl-3-isoxazolyl)ethanone or diethyl acetylenedicarboxylate using a synthetic utility of tetrasulfur tetranitride antimony pentachloride (S4N4·SbCl5) complex to make a 1,2,5-thiadiazole ring. 相似文献
62.
Rushdi I. Yousef Tobias Rüffer Harry Schmidt Dirk Steinborn 《Journal of organometallic chemistry》2005,690(5):1178-1191
MgMe2 (1) was found to react with 1,4-diazabicyclo[2.2.2]octane (dabco) in tetrahydrofuran (thf) yielding a binuclear complex [{MgMe2(thf)}2(μ-dabco)] (2). Furthermore, from reactions of MgMeBr with diglyme (diethylene glycol dimethyl ether), NEt3, and tmeda (N,N,N′,N′-tetramethylethylenediamine) in etheral solvents compounds MgMeBr(L), (L = diglyme (5); NEt3 (6); tmeda (7)) were obtained as highly air- and moisture-sensitive white powders. From a thf solution of 7 crystals of [MgMeBr(thf)(tmeda)] (8) were obtained. Reactions of MgMeBr with pmdta (N,N,N′,N″,N″-pentamethyldiethylenetriamine) in thf resulted in formation of [MgMeBr(pmdta)] (9) in nearly quantitative yield. On the other hand, the same reaction in diethyl ether gave MgMeBr(pmdta) · MgBr2(pmdta) (10) and [{MgMe2(pmdta)}7{MgMeBr(pmdta)}] (11) in 24% and 2% yield, respectively, as well as [MgMe2(pmdta)] (12) as colorless needle-like crystals in about 26% yield. The synthesized methylmagnesium compounds were characterized by microanalysis and 1H and 13C NMR spectroscopy. The coordination-induced shifts of the 1H and 13C nuclei of the ligands are small; the largest ones were found in the tmeda and pmdta complexes. Single-crystal X-ray diffraction analyses revealed in 2 a tetrahedral environment of the Mg atoms with a bridging dabco ligand and in 8 a trigonal-bipyramidal coordination of the Mg atom. The single-crystal X-ray diffraction analyses of [MgMe2(pmdta)] (12) and [MgBr2(pmdta)] (13) showed them to be monomeric with five-coordinate Mg atoms. The square-pyramidal coordination polyhedra are built up of three N and two C atoms in 12 and three N and two Br atoms in 13. The apical positions are occupied by methyl and bromo ligands, respectively. Temperature-dependent 1H NMR spectroscopic measurements (from 27 to −80 °C) of methylmagnesium bromide complexes MgMeBr(L) (L = thf (4); diglyme (5); NEt3 (6); tmeda (7)) in thf-d8 solutions indicated that the deeper the temperature the more the Schlenk equilibria are shifted to the dimethylmagnesium/dibromomagnesium species. Furthermore, at −80 °C the dimethylmagnesium compounds are predominant in the solutions of Grignard compounds 4-6 whereas in the case of the tmeda complex7 the equilibrium constant was roughly estimated to be 0.25. In contrast, [MgMeBr(pmdta)] (9) in thf-d8 revealed no dismutation into [MgMe2(pmdta)] (12) and [MgBr2(pmdta)] (13) even up to −100 °C. In accordance with this unexpected behavior, 1:1 mixtures of 12 and 13 were found to react in thf at room temperature yielding quantitatively the corresponding Grignard compound 9. Moreover, the structures of [MgMeBr(pmdta)] (9c), [MgMe2(pmdta)] (12c), and [MgBr2(pmdta)] (13c) were calculated on the DFT level of theory. The calculated structures 12c and 13c are in a good agreement with the experimentally observed structures 12 and 13. The equilibrium constant of the Schlenk equilibrium (2 9c ? 12c + 13c) was calculated to be Kgas = 2.0 × 10−3 (298 K) in the gas phase. Considering the solvent effects of both thf and diethyl ether using a polarized continuum model (PCM) the corresponding equilibrium constants were calculated to be Kthf = 1.2 × 10−3 and Kether = 3.2 × 10−3 (298 K), respectively. 相似文献
63.
64.
The thermal degradation of poly-2,2′,3,3′,4,4′,5,5′,6,6′,7,7′,7″-tridecafluoroheptylacrylate and poly-2,2′,3,3′,4,4′,5,5′,6,6′,7,7′-dodecafluoroheptylmethacrylate has been studied in isothermal conditions at 450-750 °C using pyrolysis-gas chromatography. The type and composition of the pyrolysis products give useful information about mechanism of thermal degradation. It was shown that the main thermal degradation process for both polymers is random main-chain scission. The major degradation products for fluorinated polyacrylate are monomer, dimer, saturated diester, trimer, and corresponding methacrylate. The fluorinated polymethacrylate gives monomer as the main product of thermal destruction. As a result of side-chain reaction, the thermal degradation of the fluorinated polyacrylate also produces remarkable amounts of alcohol. On the other hand, the respective alcohol is only a minor component among the pyrolysis products of the fluorinated polymethacrylate. For both polymers, the main nontrivial degradation product coming from the alkyl ester decomposition is the corresponding fluorinated cyclohexane. The formation of the fluorinated cyclohexanes may be accounted for a nucleophilic bimolecular substitution pathway. 相似文献
65.
Bistatic scattering by arbitrarily shaped objects with rough surface at optical and infrared frequencies 总被引:2,自引:0,他引:2
The scattering cross sections for arbitrarily shaped dielectric objects with rough surface are determined for optical and infrared frequencies using the Kirchhoff approximation. The formula of the coherent scattering cross section is derived, and numerical method of incoherent scattering cross section is given. As a specific example, the infrared laser scattering cross sections of rough spheres are calculated at 1.06 m. 相似文献
66.
Panchami Prabhakaran 《Tetrahedron letters》2007,48(10):1725-1727
In this Letter, we describe the unexpected reaction pattern of N,N′N″-tri-Boc-guanidine (TBG) with amines at room temperature and under reflux conditions affording N-substituted guanidines and amidinoureas, potentially important compounds with extensive applications in medicinal chemistry. This investigation shows that TBG is an excellent, readily available common starting material for the synthesis of various N-alkyl guanidines as well as N-alkyl-N′-substituted amidinoureas by simply manipulating the reaction conditions. 相似文献
67.
We have prepared SrFe2/3B″1/3O3 (B″=Mo, U, Te, and W) double perovskites in polycrystalline form by ceramic methods. Phases with B″=U, Te and W have been studied by X-ray powder diffraction and the results have been compared with neutron diffraction data available for B″=Mo. At room temperature, the stoichiometric samples crystallize in the tetragonal crystal system (space group I4/m, Z=4). Cell parameters when B″=U, Te and W are a=5.6936(1) Å, c=8.0637(1)Å; a=5.5776(1) Å, c=7.9144(3) Å and a=5.5707(3) Å, c=7.9081(5) Å, respectively.The Mössbauer spectra at room temperature for all compounds show hyperfine parameters belonging to two Fe3+ sites located at lattice positions with different degrees of distortion. This is in agreement with diffraction data that indicate that the series of compounds display different degrees of Fe-site disorder, which increases in the following sequence: Mo<U<Te<W. 相似文献
68.
This study has presented a performance investigation of an advanced tracked prime mover for the operation of agricultural goods and other operations on peat terrain. The maximum and continuous traction torque of the prime mover has been developed by designing an advanced controller for controlling the intelligent system. The prime mover’s mobility is studied with ultrasonic displacement sensor, torque transducer, National Instrument cRIO-9004 Compact-RIO Real-time Controller Unit (RCU), a National Instrument TPC 2106T Touch Panel Control (TPC), a Trimble AG132 GPS antenna and receiver unit, and a Dlink DIR-655 router. The fuzzy logic controller (FLC) has been equipped with the prime mover hydraulic system to increase the traction torque of the hydraulic motor when the prime mover’s sinkage is more than or equal to 70 mm. The prime mover’s design demonstrates good potential in traversing peat terrain as the measured tractive effort was found to be 48% of the vehicle’s gross weight while the recommended tractive effort is in the range of 30–36% of the vehicle’s gross weight. 相似文献
69.
B.T. Luke 《SAR and QSAR in environmental research》2013,24(1):41-57
While quantitative structure-activity relationships attempt to predict the numerical value of the activities, it is found that statistically good predictors do not always do a good job of qualitatively determining the activity. This study shows how Fuzzy classifiers can be used to generate Fuzzy structure-activity relationships which can more accurately determine whether or not a compound will be highly inactive, moderately inactive or active, or highly active. Four examples of these classifiers are presented and applied to a well-studied activity dataset. 相似文献
70.
《International Journal of Approximate Reasoning》2014,55(7):1606-1608
This note replies to comments made on our contribution to the Low Quality Data debate. 相似文献